Azo dyestuffs



Patented Oct. 17, 1939 2,176,521 AZO DYESTUFFS Grald Bonhfite, Basel, and Carl Apotheker,

Riehen, Switzerland,

assignors to the firm Society of Chemical Industry in Basle, Basel,

Switzerland No Drawing. Application June 28, 1938, Serial No. 216,851. In Switzerland June 30, 1937 7 Claims.

ortho-hydroxylated or ortho-carboxylated diazocompounds which lead to products capable of conversion into metalliferous dyestufis in substance'or on the fibre.

The main value of the new dyestufis resides, however, in the unexpected property of the fundamental new hydroxylated 2'-aryl-pseudona'ph'- thazimides of having affinity' in 'a causticjalka line liquor for cellulosic fibres, for instance cot ton, hemp, ramie, artificial silk from regenerated cellulose or thelike. If, for example, the fibre treated with the hydroxylated '2'-aryl-pseudonaphthazimide is developed with the above indicated non-sulfonated diazo-compounds, there are produced color tints which are characterized both by their intensity and by their excellent properties of fastness. Among the diazo-compounds suitable for the purpose are, for instance, those Whi0h are derived from aniline, ethers and. esters of aminophenols, for instance 2:5 dichloraniline, 1-amino-2-methoXy-5nitrobenzene, l-chloraminodiphenyl ether, 4:4'-dichloraminodiphenyl ether; from mono-acylation products of 2:5-di- 'aminohydroquinone diethyl ether or dimethyl ether and benzoyl chloride or phenoxyacetic acid chloride, amino-azo-dyestuffs, for instance 4-amino-5-methoxyazobenzene, 4-amino-2z5-dimethoxyazob enzene, 4 4 -diamino-2-methyl-5-meth- 'oxyazobenzene; also from chlorotoluidines, for instance l-chloro-Z-methyl-1-aminobenzene,from nitranilines, for instance 4-chloro-1-amino-2- nitro-benzene or 4-nitro-2-methoxy-l-aminobenzene, aor p-naphthylamines or the like.

duced; especially valuable are the dyestuffs from The new dyestufis correspond therefore to the general formula I y IITN R wherein R stands for an aromatic radical selected from the group consisting of aromatic radicals of the benzene and naphthalene series, two ws stand for hydrogen atoms and one :1: stands for a hydroxyl group, the two ys which stand in orthoposition to hydrogen atoms standing also for hydrogen atoms and the 11 standing in ortho-position to a hydroxy group standing for a radical -N=N--R1, in which R1 stands for an aromatic radical selected from the group consisting of aromatic radicals of the benzene and naphthalene series, which products are dark powders which, when produced on the vegetable fiber dye the same reddish-yellow to red, violet, blue, brown and black tints. Among these dyestufis those are inter alia particularly valuable which correspond to the general formula N=N-Bi T III-N v R wherein R stands for an aromatic radical of the benzene series and R1 stands for an aromatic radical of the benzene series which is substituted in para-position to the --N=N group by a radical of the general formula V ITFRR in which R2 stands for a radical selected from the group consisting of benzoyl and phenoxy acetyl radicals. This is due to the beautiful it soda lye of 30 per cent strength, 15 parts of calbrown tints which they produce on the vegetable fiber. The dyestuffs of the general formula a beautiful brown color of very good properties of fastness. The new dyestuff corresponds very N=N-R probably to the formula I OCH:

N H t I OCH: N-1 I R are also of particular interest on account of their N clear tints. I

It has also been found that the non-sulfonated NN 2'-arylpseudonaphahazimides hydroxylated in 1*" the 2-position of the naphthalene nucleus may be obtained in a very smooth way by subjecting to fusion with alkali a pseudo-azimidosulfonic acid obtainable by oxidizing the ortho-ami'noazo-dya stuff from any diazo-compound and an amino naphthalene-5-mono-sulfonic acid which couples in ortho-position to the amino-group with diazocompounds.

Further data on the production of these azimides are contained in the copending application Serial No. 216,350, filed June 28, 1938.

The result of this process is quite surprising, because it was to be supposed that at the very high temperature which must be used in order to convert the mono-sulfonic acid into the hydroxyl compound there would be a deeply seated decomposition of the molecule. The same or isomeric azimides are obtained by the action of a diazo-compound on ,6-amino-B-hydroxynaphthalane in acid medium and treating the orthoaminoazo-dyestuif thus produced with an oxidizing agent. V

The following examples illustrate the invention the parts being by weight:

Example 1 16.2 parts of 2:5-dichlorani1ine are diazotized as usual and the product is introduced into a solution of 26.1 parts of 2-hydroXy-2-phenyl- 5:6-pseudonaphthazimide, 20 parts of caustic When produced on the fibre the dyestufi of Example 1 yields an orange tint. The substitution of 5-nitro-anisidine (OCI-I3:NI-I2:NO2=1:2:5) for the 2:5-dichloroani1ine leads to a redder tint, whereas diazo-p-naphthalene leads to a red tint. Similar dyestuffs are obtained when instead of the 2-hydroXy-2'-phenyl-5 6. pseudonaphthazimide there are used other 2-hydroxy-5z6-pseudonaphthazimides arylated in 2-position, for instance 2'-(4"-methyl)'-,, 2-(4-methoxy), 2'- (2-methyl) 2'-(2" -ethoxy) or 2'-(2"methyD-phenyl derivatives or ZT-a-naphthyl or [3- naphthyl derivatives.

Example 3 Cotton yarn is impregnated with a solution of 5 grams of 2-hydroxy-2' (4"-chloro) -phenyl- 5:6-pseudonaphthazimide, 7 cc. of caustic soda solution of 36 B., 5 cc. of Turkey red oil, 25 grams of sodium chloride per litre at C., then well wrung out and developed in a diazo-solution buffered with sodium acetate, corresponding with 2 grams of 4-(4'-methyl)-phenoxyacetylamino- 2z5-dimethoxy-l-aminobenzene per litre. There is produced a very fine brown tint of very good properties of fastness. Similar brown tints are obtained, for example, with the 1-amino-2z5-diethoxyor -dimethoxy-4-benzoylaminobenzene or 4-(4'- or 2'-methyl)-phenoXy-acetylamino- 2:5-diethoxybenzene. Such a dyestuff has for cined sodium carbonate and 500 parts of water. The dyestuif of the formula example the formula N=N OCH;

OH 0. W0

OH CH:

immediately separates in the form of an orange precipitate which is filtered and dried.

Example 2 ill The isomeric dyestuffs which are derived from the '7 :8-pseudo-naphthazimides, for example dyestuffs of the formula (ROE;

have similar tints. The same applies to the corresponding dyestufis in which the benzoyl group of the diazotizing components is replaced by a phenoxyacetyl group.

Example 4 Example 5 Cotton yarn is impregnated with a solution of 6 grams of 2-hydroxy-2'-phenyl-3:-pseudonaphthazimide, '7 cc. of caustic soda solution of 36 B., 5 cc. of Turkey red oil and 25 grams of a sodium chloride per litre at 70 C. It is then well good properties of fastness.

wrung out and developed in a diazo-solution, bufiered with sodium acetate corresponding with 2 grams 2:5-dichloraniline per litre. There is produced a very pure gold orange tint of very The new dyestuff corresponds very probably to the formula Such dyestuffs are for example the products, of the formulas (R=phenyl or CI-Iz-O-phenyl).

What we claim is:

1. As new dyestuffs, the products of the general formula wherein R. stands. for an aromatic radical selected from the group consisting or aromatic radicals of the benzene and naphthalene series, two :Bs stand for hydrogen atoms and one :1: stands for a hydroxyl group, the two ys which stand in ortho-position to hydrogen atoms standing also for hydrogen atoms and the 11 standing in orthoposition to a hydroxyl group standing for a radical N=NR1, in which R1 stands for an aromatic radical selected from the group consisting of aromatic radicals of the benzene and naphthalene series, whichl products aredark powders which when produced on the vegetable fiber dye the same reddish yellow to red, violet, blue, brown and black tints of good fastness.

2. As new dyestuffs, the products of the general formula wherein R stands for an aromatic radical of the benzene series, two ms stand for hydrogen atoms and one 1: stands for a hydroxyl group, the two ys which stand in o-rtho-position to hydrogen atoms standing also for hydrogen atoms and the y standing in ortho-position to a hydroxy group standing for a radical -N=NR1, in

which R1 stands for an aromatic radical se-.

lected from the group consisting of aromatic radicals of the benzene and naphthalene series, which products are dark powders which, when produced on the vegetable fiber dye the same reddish yellow to red, violet, blue, brown and black tints of good fastness.

3. As new dyestufis, the products: of the general formula III-N R wherein R and R1 stand for aromatic radicals of the benzene series, which products are dark powders which when produced on the vegetable fiber dye the same reddish yellow to red and brown tints of good fastness.

5. As new dyestufis, the products of the general formula in which R2 stands for a radical selected from the group consisting of benzoyl and phenoxy acetyl radicals, which products are dark powders which when produced .on the vegetable fiber dye the same fast brown tints of good fastness.

6. The dyestuif of the formula OCZH5 ii 1 N 7. The dyestufi of the formula W ?O2H5 (fH;

Ti IIIN GERALD BONHOTE.

CARL APOTI-IEKER. 

